This paper describes the construction of hemiacetal 2, the core of pseudolaric acid A via oxidative cleavage of acetonide 6 or 7 and enolization-hemiacetalization of aldehyde 8. A plausible general mechanism for thc i...This paper describes the construction of hemiacetal 2, the core of pseudolaric acid A via oxidative cleavage of acetonide 6 or 7 and enolization-hemiacetalization of aldehyde 8. A plausible general mechanism for thc intramolecular [4+3] cycloaddition of sulfoxide 4 to adduct 3 is suggested.展开更多
Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks ...Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks has evoked considerable interest in the field of chemistry.Among the various approaches,organocatalytic asymmetric(4+3)cycloadditions are highly effective for the enantioselective construction of seven-membered rings.Over the past two decades,substantial efforts have been devoted to this field and chemists have developed various organocatalytic asymmetric(4+3)cycloadditions.This review summarizes the progress in organocatalytic asymmetric(4+3)cycloadditions from 2003 to early 2022 and provides insights into challenging issues faced in this research field,enabling the future development of this field.展开更多
We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azoci...We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azocines and furo[3,2-b]azocines with good to excellent yields(up to 96%)and exclusive regioselectivities.This methodology featured mild reaction conditions and good functional group tolerance.The synthetic utility was demonstrated by a gram-scale reaction.Furthermore,the catalytic asymmetric[4+4]cycloaddition version has also been explored.展开更多
An unprecedent[4+3]cycloaddition of furoketenimines with furocarbenoids has been disclosed for the divergent and efficient synthesis of cycloheptafuran and cycloheptapyrrole scaffolds.Zinc chloride acted as promoters ...An unprecedent[4+3]cycloaddition of furoketenimines with furocarbenoids has been disclosed for the divergent and efficient synthesis of cycloheptafuran and cycloheptapyrrole scaffolds.Zinc chloride acted as promoters for both the formation of these two transient intermediates from isocyanides and ene-yne-ketones,and the subsequent construction of seven-membered ring.Three rings and five bonds were constructed successively in this three-component one-pot domino reaction.展开更多
The first diastereodivergent formal[4+1]cycloaddition reactions of azoalkenes with p-quinone methides(pQMs)have been accomplished.The reported reaction occurred via a domino oxa-1,4-addition/1,6-addition process,allow...The first diastereodivergent formal[4+1]cycloaddition reactions of azoalkenes with p-quinone methides(pQMs)have been accomplished.The reported reaction occurred via a domino oxa-1,4-addition/1,6-addition process,allowing the use of common azoalkenes as C1 synthons.A broad range of 2,3-dihydrobenzofurans was smoothly prepared in good yields and with reversible diastereoselectivities.The steric hindrance and hydrogenbonding interaction were proposed to account for the two different modes of diastereo-control.The projected reaction features the employment of azoalkene as carbene-like C1 synthon,mild conditions,broad substrate scope and tunable diastereoselectivity.展开更多
A palladium-catalyzed diastereo-and enantioselective all carbon [4+3] cycloaddition of trimethylenemethane was developed by employing the elaborate tetrahydroquinoline-derived phosphoramidite ligand. The exclusive reg...A palladium-catalyzed diastereo-and enantioselective all carbon [4+3] cycloaddition of trimethylenemethane was developed by employing the elaborate tetrahydroquinoline-derived phosphoramidite ligand. The exclusive regioselectivity was realized by using the aromatization-driven diene indole-2,3-quinodimethanes, affording biologically important cyclohepta[b]indoles with excellent diastereo-, and enantioselectivities(up to >20:1 dr, >99% ee). Furthermore, the more challenging pyrrolidone-3,4-dienes, in the absence of aromatization force, were also compatible inthereaction, providing novel cyclohepta[c]pyrrol-1(2H)-ones with excellent regio-, diastereo-, and enantioselectivities(up to >20:1 rr, >20:1 dr, >99% ee).展开更多
A Pd-catalyzed asymmetric decarboxylative[4+2]cycloaddition of 3-nitroindoles and vinyl benzoxazinanones is developed through a dearomatization approach.The reaction provides an efficient protocol for constructing a s...A Pd-catalyzed asymmetric decarboxylative[4+2]cycloaddition of 3-nitroindoles and vinyl benzoxazinanones is developed through a dearomatization approach.The reaction provides an efficient protocol for constructing a series of chiral tetrahydro-5H-indolo[2,3-b]quinolines in high yields and with excellent diastereo-and enantioselectivities.展开更多
Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The...Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The structures of the two compounds synthesized herein were fully confirmed by 1HNMR,,(13)C NMR,and MS(ESI).The thermal analysis showed that the mass losses of the synthesized compounds 4 and 5 containing 1,2,3-triazole groups are similar to each other.展开更多
Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their ...Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks.The cycloadducts,ultimately derived from furfural,a renewal chemical feedstock,are obtained with up to 4:1 dr and with ee retained from the epoxide.展开更多
A CuSO_4 catalyzed ynamide formation/[4+2] cycloaddition relay reaction was achieved in one-pot.Various 4,7-cis-dihydroindolines were produced in good to high yields. The one-pot operation in conjunction with the chea...A CuSO_4 catalyzed ynamide formation/[4+2] cycloaddition relay reaction was achieved in one-pot.Various 4,7-cis-dihydroindolines were produced in good to high yields. The one-pot operation in conjunction with the cheap and benign copper catalysis renders this reaction highly sustainable.展开更多
A new DBU-catalyzed formal[4+2]cycloaddition between ortho-hydroxyphenyl-substituted para-quinone methides and electron-deficient dienophiles including 3-methyleneoxindoles and 2-aryldeneindene-1,3-diones was establis...A new DBU-catalyzed formal[4+2]cycloaddition between ortho-hydroxyphenyl-substituted para-quinone methides and electron-deficient dienophiles including 3-methyleneoxindoles and 2-aryldeneindene-1,3-diones was established.A wide range of functionalized spiro[chromane-3,30-indolines]and spiro[chromane-3,20-indenes]were successfully synthesized in good yields and with high diastereoselectivity.The features of the reaction included readily available substrates,mild reaction conditions,convenient methodology and good functional group tolerance.展开更多
A Lewis acid-catalyzed[4+2]cycloaddition of 3-alkyl-2-vinylindoles withβ,γ-unsaturatedα-ketoesters has been established in the presence of Sc(OTf)3,which afforded a series of indole-containing pyran derivatives in ...A Lewis acid-catalyzed[4+2]cycloaddition of 3-alkyl-2-vinylindoles withβ,γ-unsaturatedα-ketoesters has been established in the presence of Sc(OTf)3,which afforded a series of indole-containing pyran derivatives in generally good yields(up to 90%yield)with excellent diastereoselectivities(up to >95:5 dr)under mild conditions.This approach not only enriches the chemistry of 3-alkyl-2-vinylindoles,but also has provided an atom-economic method for the synthesis of indole-containing pyran derivatives with potential bioactivity.展开更多
Herein,a DMAP-catalyzed[4+2]annulation ofα-substituted allenoates with arylazosulfones is reported,which affords facile access to tetrahydropyridazine derivative in synthetically useful yields.This reaction features ...Herein,a DMAP-catalyzed[4+2]annulation ofα-substituted allenoates with arylazosulfones is reported,which affords facile access to tetrahydropyridazine derivative in synthetically useful yields.This reaction features mild conditions and good functional group tolerance.Moreover,the resultant products can be readily transformed into pyridazin-3-one derivatives in the presence of DDQ.展开更多
A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad re...A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad reaction scope.Based on mechanism studies,it is believed that the palladiumcatalyzed [4+1] imidoylative cycloaddition of prop-2-yn-1-ones was concerted.Treated with a ryl amine and H_2 O,the [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides provided 2-amino-4-amidylpyrroles efficiently.展开更多
o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused o...o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4+2]/[2+2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science.展开更多
基金the National Natural Science Foundation of China.
文摘This paper describes the construction of hemiacetal 2, the core of pseudolaric acid A via oxidative cleavage of acetonide 6 or 7 and enolization-hemiacetalization of aldehyde 8. A plausible general mechanism for thc intramolecular [4+3] cycloaddition of sulfoxide 4 to adduct 3 is suggested.
基金supported by the National Natural Science Foundation of China(22125104,21831007)the Natural Science Foundation of Jiangsu Province(BK20210916)the High Education Natural Science Foundation of Jiangsu Province(21KJB150009)。
文摘Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks has evoked considerable interest in the field of chemistry.Among the various approaches,organocatalytic asymmetric(4+3)cycloadditions are highly effective for the enantioselective construction of seven-membered rings.Over the past two decades,substantial efforts have been devoted to this field and chemists have developed various organocatalytic asymmetric(4+3)cycloadditions.This review summarizes the progress in organocatalytic asymmetric(4+3)cycloadditions from 2003 to early 2022 and provides insights into challenging issues faced in this research field,enabling the future development of this field.
基金We are grateful for financial support from National Key Research and Development Program of China(2021YFA0804900)the NSFC(22171082,21971062)+1 种基金the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2022R01007)Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism.
文摘We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azocines and furo[3,2-b]azocines with good to excellent yields(up to 96%)and exclusive regioselectivities.This methodology featured mild reaction conditions and good functional group tolerance.The synthetic utility was demonstrated by a gram-scale reaction.Furthermore,the catalytic asymmetric[4+4]cycloaddition version has also been explored.
基金financial support from National Natural Science Foundation of China(Nos.22171168,22001152 and 22101159)Taishan Scholar Program of Shandong Province and the Natural Science Foundation of Shandong Province of China(No.ZR2020QB019)。
文摘An unprecedent[4+3]cycloaddition of furoketenimines with furocarbenoids has been disclosed for the divergent and efficient synthesis of cycloheptafuran and cycloheptapyrrole scaffolds.Zinc chloride acted as promoters for both the formation of these two transient intermediates from isocyanides and ene-yne-ketones,and the subsequent construction of seven-membered ring.Three rings and five bonds were constructed successively in this three-component one-pot domino reaction.
基金support from the Natural Science Foundation of Henan Province(No.222300420084)the Application Research Plan of Key Scientific Research Projects in Colleges and Universities of Henan Province(No.22A150056)is gratefully acknowledged.
文摘The first diastereodivergent formal[4+1]cycloaddition reactions of azoalkenes with p-quinone methides(pQMs)have been accomplished.The reported reaction occurred via a domino oxa-1,4-addition/1,6-addition process,allowing the use of common azoalkenes as C1 synthons.A broad range of 2,3-dihydrobenzofurans was smoothly prepared in good yields and with reversible diastereoselectivities.The steric hindrance and hydrogenbonding interaction were proposed to account for the two different modes of diastereo-control.The projected reaction features the employment of azoalkene as carbene-like C1 synthon,mild conditions,broad substrate scope and tunable diastereoselectivity.
基金supported by the National Natural Science Foundation of China (21772038, 21971062)。
文摘A palladium-catalyzed diastereo-and enantioselective all carbon [4+3] cycloaddition of trimethylenemethane was developed by employing the elaborate tetrahydroquinoline-derived phosphoramidite ligand. The exclusive regioselectivity was realized by using the aromatization-driven diene indole-2,3-quinodimethanes, affording biologically important cyclohepta[b]indoles with excellent diastereo-, and enantioselectivities(up to >20:1 dr, >99% ee). Furthermore, the more challenging pyrrolidone-3,4-dienes, in the absence of aromatization force, were also compatible inthereaction, providing novel cyclohepta[c]pyrrol-1(2H)-ones with excellent regio-, diastereo-, and enantioselectivities(up to >20:1 rr, >20:1 dr, >99% ee).
基金financial support from the National Natural Science Foundation of China (NSFC, Nos. 21772215, 21532010 and 21472214)the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20030100)+2 种基金the Chinese Academy of Sciencesthe Technology Commission of Shanghai Municipalitythe Croucher Foundation of Hong Kong
文摘A Pd-catalyzed asymmetric decarboxylative[4+2]cycloaddition of 3-nitroindoles and vinyl benzoxazinanones is developed through a dearomatization approach.The reaction provides an efficient protocol for constructing a series of chiral tetrahydro-5H-indolo[2,3-b]quinolines in high yields and with excellent diastereo-and enantioselectivities.
基金the financial supports of the National Natural Science Foundation of China(No.21102003)Scientific Research Foundation for the Introduction of Talent and Young Teachers Scientific Research Foundation of Anhui University of Science & Technology(Nos.11214,2012QNY27)
文摘Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The structures of the two compounds synthesized herein were fully confirmed by 1HNMR,,(13)C NMR,and MS(ESI).The thermal analysis showed that the mass losses of the synthesized compounds 4 and 5 containing 1,2,3-triazole groups are similar to each other.
基金supported by the Research Grants Council General Research Fund (No. 17301314)
文摘Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks.The cycloadducts,ultimately derived from furfural,a renewal chemical feedstock,are obtained with up to 4:1 dr and with ee retained from the epoxide.
基金the National Natural Science Foundation of China (No. 21672027)QingLan Project of Jiangsu Province (2016)SixTalent-Peaks Program of Jiangsu (2016) for financial support
文摘A CuSO_4 catalyzed ynamide formation/[4+2] cycloaddition relay reaction was achieved in one-pot.Various 4,7-cis-dihydroindolines were produced in good to high yields. The one-pot operation in conjunction with the cheap and benign copper catalysis renders this reaction highly sustainable.
基金We are grateful to the National Natural Science Foundation of China(Nos.21572196,21871227)the Priority Academic Program Development of Jiangsu Higher Education Institutions(No.BK2013016)for financial support.
文摘A new DBU-catalyzed formal[4+2]cycloaddition between ortho-hydroxyphenyl-substituted para-quinone methides and electron-deficient dienophiles including 3-methyleneoxindoles and 2-aryldeneindene-1,3-diones was established.A wide range of functionalized spiro[chromane-3,30-indolines]and spiro[chromane-3,20-indenes]were successfully synthesized in good yields and with high diastereoselectivity.The features of the reaction included readily available substrates,mild reaction conditions,convenient methodology and good functional group tolerance.
基金This work was supported by National Natural Science Foundation of China(No.21772069)Natural Science Foundation of Jiangsu Province(No.BK20201018)+1 种基金Undergraduate Students Project of Jiangsu Province(No.202010320050Z)High-level Innovative and Entrepreneurial Talents Introduction Plan of Jiangsu Province,and Natural Science Foundation of JSNU(No.19XSRX010).
文摘A Lewis acid-catalyzed[4+2]cycloaddition of 3-alkyl-2-vinylindoles withβ,γ-unsaturatedα-ketoesters has been established in the presence of Sc(OTf)3,which afforded a series of indole-containing pyran derivatives in generally good yields(up to 90%yield)with excellent diastereoselectivities(up to >95:5 dr)under mild conditions.This approach not only enriches the chemistry of 3-alkyl-2-vinylindoles,but also has provided an atom-economic method for the synthesis of indole-containing pyran derivatives with potential bioactivity.
基金the Independent Research Foundation of Key Laboratory of Green and Precise Synthetic Chemistry and Applications in Huaibei Normal University,Ministry of Educationthe University Top Talents Academic Funding Project of Anhui Province(gxbjzD2021097)+1 种基金the Natural Science Foundation of Educational Committee from Anhui Province and Huaibei Normal University(KJ2020A0045,KJ2020A1199,KJ2020B01,2023ZK078,2023ZK079)the University Synergy Innovation Program of Anhui Province(GXXT-2020-078)for financial support of this work.
文摘Herein,a DMAP-catalyzed[4+2]annulation ofα-substituted allenoates with arylazosulfones is reported,which affords facile access to tetrahydropyridazine derivative in synthetically useful yields.This reaction features mild conditions and good functional group tolerance.Moreover,the resultant products can be readily transformed into pyridazin-3-one derivatives in the presence of DDQ.
基金Financial supports from the Natural Science Foundation of Shandong Province(Nos.ZR2019PB004 and ZR2018BB029)the Natural Science Foundation of China(Nos.21502069 and 21772067)are gratefully acknowledged。
文摘A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad reaction scope.Based on mechanism studies,it is believed that the palladiumcatalyzed [4+1] imidoylative cycloaddition of prop-2-yn-1-ones was concerted.Treated with a ryl amine and H_2 O,the [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides provided 2-amino-4-amidylpyrroles efficiently.
文摘o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4+2]/[2+2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science.